Nitrogen atom transfer

ABSTRACT

Process and apparatus for addition of nitrogen to an organic molecule under electrochemical conditions. Processes include aziridination of olefins and imination of sulfoxides to form sulfoximines. Nitrene generation in the presence of a carboxylate is described

FIELD OF THE INVENTION

This invention is in the field of electrochemical atom transfer,particularly the introduction of a nitrogen atom into an organicmolecule in an electrochemical process.

BACKGROUND OF THE INVENTION

The reactions of organic compounds can be classified into two broadcategories: carbon-carbon bond forming processes and reactions in whichcarbon atoms change their oxidation states (redox processes). The redoxreactions in nature are accomplished by the enzyme molecules. Thesecatalysts contain metal centers that carry out the requisite electronand/or atom transfer reactions. Over the years, remarkable progress hasbeen achieved in design and applications of novel metal-based complexes.The metal center of a synthetic catalyst is surrounded by a smallmolecule ligand that often resembles and emulates the catalytic reactionsite of an enzyme. One of the key roles of the ligand is to modulatereactivity at the metal center. This permits the reactivity of the metalion in a given oxidation state to be adjusted to control the steric andelectronic parameters of a given reaction. This strategy has been shownto adequately address the issues of regio-, chemo-, andstereoselectivity of a number of widely used synthetic transformations.The judicious choice of stoichiometric reductant or oxidant is requiredin order to render a given reaction catalytic in the metal reagent.

Aziridination of olefins is of particular current interest due to theenormous synthetic potential of aziridines.¹ These nitrogen-containingheterocycles have 28 kcal/mol of strai² and are amenable to ring-openingreactions with a wide range of nucleophiles. Such transformations leadto molecules with valuable 1,2-heteroatom relationships, commonly foundin natural products and in pharmaceuticals.³ Olefin aziridinationreactions are usually accomplished via metal-mediated transfer of anitrene fragment to the olefin.⁴ The corresponding processes can producea variety of by-products that stem from metal additives and fromoxidants. To date, there are no examples of catalytic oxidation systemsbased on readily available oxidants that convert simple amines or amidesinto active nitrogen transfer species in the presence of olefins andleave no by-products.

A synthetically attractive route is the aziridination of olefins withN-aminophthalimide and lead tetraacetate as oxidant (eq. 1).⁵ However,its widespread application is hampered by the use of large amounts ofPb(OAc)₄, known for its high toxicity.⁶

SUMMARY OF THE INVENTION

This invention provides an electrochemical process by which a neworganic molecule is obtained through the formation of a nitrogen bond.An example is the formation of an aziridine by addition of the nitrogenacross a double bond between two carbon atoms, in which two C—N bondsform. Another example is formation of a sulfoxime by addition of thenitrogen to the sulfur atom of a sulfoxide, in which a S═N bond forms.The results of the various addition reactions shown herein can beexplained in terms of the formation of a nitrene intermediate formedunder the electrochemical conditions of the invention.

In one aspect, the invention is an electrochemical process for theformation of a compound having formula I:

The process includes a step of contacting a compound having formula IIand a compound having formula III with each other in an electrolyticcell under conditions of electrolysis sufficient to form the compound offormula I.

“A” shown in these formulae is selected from the group consisting of C,N and O, and

-   -   (i) when A is a carbon atom, each of R₁, R₂, R₃, and R is        hydrogen or an organic group;    -   (ii) when A is a nitrogen atom, each of R₁, R₂, and R₃, is        hydrogen or an organic group, and R₄ is an electron pair;    -   (iii) when A is an oxygen atom, each of R₁ and R₂ is hydrogen or        an organic group, and each of R₃ and R₄ is an electron pair; and    -   (iv) R₅ is NR₆R₇ and each of R₆ and R₇ is an organic group.

A is preferably a carbon atom, but it can be a nitrogen atom, or anoxygen atom.

The group from which each of R₁, R₂, R₃, and R₄ may be selected can bethe group consisting of alkyl, alkenyl, alkynyl, aryl, phenyl, biphenyl,and substituted alkyl, alkenyl, alkynyl, aryl, wherein the substituentsare selected from the group of alkyl, alkenyl, alkynyl, aryl, halide,ketone, aldehyde, alcohol, ether, ester, carboxylic acid, primary amino,secondary amino, tertiary amino, amide, nitrile, nitro, epoxide, imine,aziridine, sulfone, phosphone, and silane.

In another aspect, the group from which each of R₁, R₂, R₃, and R₄ maybe selected is the group consisting of alkyl, alkenyl, alkynyl, aryl,and substituted alkyl, alkenyl, alkynyl, aryl, wherein the substituentsare selected from the group of alkyl aryl, halide, ketone, aldehyde,alcohol, ether, ester, carboxylic acid, primary amino, secondary amino,tertiary amino, amide, nitro, epoxide, aziridine, sulfone, phosphone,and silane.

In a narrower aspect, the group from which each of R₁, R₂, R₃, and R₄may be selected can the group consisting of alkyl and aryl, andsubstituted alkyl and aryl, wherein the substituents are selected fromthe group of alkyl, aryl, halide, ketone, aldehyde, alcohol, ether,ester, carboxylic acid, primary amino, secondary amino, tertiary amino,amide, nitro, epoxide, aziridine, sulfone, phosphone, and silane.

More particularly, the substituents can be selected from the group ofhalide, ketone, alcohol and ester.

In another aspect, “A” of starting compound II is a carbon atom, (i) ifR₃ and R₄ are each hydrogen, then each of R₁ and R₂ is not hydrogen, orthe double bond shown in formula II is conjugated with another olefinicdouble bond, (ii) if a first carbon atom of the double bond shown informula II is in an α-position with respect to a carbonyl group of R₁,then the second carbon atom of the double bond is not in an α-positionwith respect to a carbonyl group of R₃, and (iii) if a first carbon atomof the double bond shown in formula II is in an α-position with respectto a carbonyl group of R₂, then the second carbon atom of the doublebond is not in an α-position with respect to carbonyl group of R₄.

In another aspect of a process of the invention, II is selected from thegroup consisting of cyclohexene, cyclohex-2-enone, 2-methyl-pent-2-ene,3-bromo-2-methyl-propene, trans-3-phenyl-acrylic acid methyl ester,cyclooctene, 2-methyl-buta-1,3-diene, trans-1,3-diphenylpropenone,trans-hex-4-en-3-one, trans-but-2-enedioic acid dimethyl ester,trans-3-phenyl-prop-2-en-1-ol, trans-4-phenyl-but-3-enoic acid methylester, 2-(acetoxy-phenyl-methyl)-acrylic acid methyl ester,2-(hydroxy-phenyl-methyl)-acrylic acid methyl ester,trans-1,4-dichlorobutene, cis-1,4 dichlorobutene,2-(phenylp-toluenesulfonamidomethyl)acrylic acid methyl ester and anyderivative thereof obtained by substitution of a hydrogen of a C—H bondwith an alkyl, phenyl, halide, ketone, aldehyde, alcohol, ether, ester,carboxylic acid, primary amino, secondary amino, tertiary amino, amide,nitro, epoxide, aziridine, sulfone, phosphone, and silane, wherein anysuch group can itself be substituted with a said group.

In a specific aspect, compound II is selected from the group consistingof cyclohexene, cyclohex-2-enone, 2-methyl-pent-2-ene,3-bromo-2-methyl-propene, trans-3-phenyl-acrylic acid methyl ester,cyclooctene, 2-methyl-buta-1,3-diene, trans-1,3-diphenylpropenone,trans-hex en-3-one, trans-but-2-enedioic acid dimethyl ester,trans-3-phenyl-prop-2-en-1-ol, trans-4-phenyl-but-3-enoic acid methylester, 2-(acetoxy-phenyl-methyl)-acrylic acid methyl ester,2-(hydroxy-phenyl-methyl)-acrylic acid methyl ester,trans-1,4-dichlorobutene, cis-1,4 dichlorobutene, and 2-(phenylp-toluenesulfonamidomethyl)acrylic acid methyl ester.

In another aspect, the invention is process for the syn-addition of anitrogen atom across a double bond.

The R₅ group of compound III, can be selected from the specific group:

wherein each of R₈, R₉, R₁₀, R₁₁, R₁₂ and R₁₃ is an organic group.

Even more specifically, each of R₈, R₉, R₁₀, R₁₁, R₁₂ and R₁₃ can beselected from the group consisting of alkyl, alkenyl, alkynyl, aryl,phenyl, biphenyl and substituted alkyl, alkenyl, alkynyl, aryl, phenyland biphenyl wherein the substituents are selected from the group ofalkyl, alkenyl, alknyl, aryl, halide, ketone, aldehyde, alcohol, ether,ester, carboxylic acid, primary amino, secondary amino, tertiary amino,amide, nitrile, nitro, epoxide, imine, aziridine, sulfone, phosphone,and silane.

In a narrower aspect of the invention, each of R₈, R₉, R₁₀, R₁₁, R₁₂ andR₁₃ can be selected from the group consisting of alkyl, aryl, phenyl andsubstituted alkyl, aryl and phenyl, wherein the substituents areselected from the group of alkyl, aryl, phenyl, halide, ketone,aldehyde, alcohol, ether, ester, carboxylic acid, primary amino,secondary amino, tertiary amino, amide, nitro, epoxide, aziridine,sulfone, phosphone, and silane Each of R₈, R₉, R₁₀, R₁₁, R₁₂ and R₁₃preferably includes up to 20 carbon atoms, more preferably up to 18carbon atoms, more preferably up to 16 carbon atoms, more preferably upto 14 carbon atoms, or up to 12 carbon atoms, or up to 10 carbon atoms,or up to 8 carbon atoms, or up to 6 carbon atoms.

Each of the substituents of the substituted groups from which R₈, R₉,R₁₀, R₁ ₁, R₁₂ and R₁₃ can be selected is preferably selected from thegroup consisting of halide, ketone, alcohol and ester, and morepreferably from halide, alcohol and ester.

In a specific aspect of the invention, the compound having formula IIIis N-aminophthalimide. Any of the four C—H bonds of this molecule can bereplaced with substituents that would not destroy the primary aminogroup of this compound to be electrochemically oxidized, i.e., alkyl,aryl, halide, alkyl halide, etc.

In another aspect of the invention, the compound having formula Im has alower oxidation potential than that of a compound having formula II. Itis also preferred that the compound having formula III is oxidized at afaster rate than a compound having formula II under the conditions ofelectrolysis of the invention.

The solvent the electrolytic cell can be a polar non-protic solvent, andparticularly wherein the solvent can be selected from the groupconsisting of dichloromethane, acetonitrile, N,N-dimethylformamide,tetrahydrofuran, nitromethane, chloroform, propylene carbonate, andmixtures thereof, or other solvent suitable for conducting anelectrochemical process of the invention.

In another aspect, the invention is an electrochemical process for theformation of a compound having formula IV,

In this aspect, the process includes contacting a compound havingformula V and a compound having formula III with each other in anelectrolytic cell under conditions of electrolysis sufficient to formthe compound of formula IV.

In the indicated formulae,

-   -   (i) B is selected from the group consisting of P, S, Se and Te;    -   (ii) each of R₁₄ and R₁₅ is hydrogen or an organic group; and    -   (iii) R₅ is NR₆R₇ and each of R and R₇ is an organic group.

The “B” is most preferably a sulfur atom, but it can be a phosphorusatom, a selenium atom, or a tellurium atom.

The group of organic groups from which each of R₁₄, and R₁₅ may beselected can be the group of alkyl, alkenyl, alkynyl, aryl, phenyl,biphenyl, and substituted alkyl, alkenyl, alkynyl, aryl, phenyl andbiphenyl wherein the substituents are selected from the group of alkyl,alkenyl, alkynyl, aryl, halide, ketone, aldehyde, alcohol, ether, ester,carboxylic acid, primary amino, secondary amino, tertiary amino, amide,nitrile, nitro, epoxide, imine, aziridine, sulfone, phosphone, andsilane.

More particularly, the group from which each of R₁₄, and R₁₅ may beselected can be the group consisting of alkyl, alkenyl, alkynyl, aryl,and substituted alkyl, alkenyl, alkynyl, aryl, wherein the substituentsare selected from the group of alkyl, aryl, halide, ketone, aldehyde,alcohol, ether, ester, carboxylic acid, primary amino, secondary amino,tertiary amino, amide; nitro, epoxide, aziridine, sulfone, phosphone,and silane.

Even more particularly, the group from which each of R₁₄, and R₁₅ may beselected is the group consisting of alkyl and aryl, and substitutedalkyl and aryl, wherein the substituents are selected from the group ofalkyl, aryl, halide, ketone, aldehyde, alcohol, ether, ester, carboxylicacid, primary amino, secondary amino, tertiary amino, amide, nitro,epoxide, aziridine, sulfone, phosphone, and silane. More particularly,wherein the substituents are selected from the group of halide, ketone,alcohol and ester, and more particularly, halide, alcohol and ester.

The invention includes a process wherein compound V is selected from thegroup consisting of compounds VIII to XV:

and any derivative of any of compounds VII to XV obtained bysubstitution of a hydrogen of a C—H bond with an alkyl, phenyl, halide,ketone, aldehyde, alcohol, ether, ester, carboxylic acid, primary amino,secondary amino, tertiary amino, amide, nitro, epoxide, aziridine,sulfone, phosphone, and silane, wherein any said group can itselfinclude such a substituent.

More specifically, compound V can be selected from any of compounds VIIIto XV.

R₅ can be selected as described above, for reaction of compound V andIII.

In a particular embodiment, the compound having formula III has a loweroxidation potential than that of a compound having formula II. Further,the compound having formula III is oxidized at a faster rate than acompound having formula II under the conditions of electrolysis.

In another aspect, the invention is an electrochemical process for theformation of a compound having formula VI:

Here, the process involves contacting a compound having formula VII anda compound having formula III with each other in an electrolytic cellunder conditions of electrolysis sufficient to form the compound offormula VI.

In this aspect of the invention,

-   -   (i) when D is a carbon atom, each of R₁₆ and R₁₇ is hydrogen or        an organic group; and    -   (ii) when D is a nitrogen atom, R₁₆ is hydrogen or an organic        group, and R₁₇ is an electron pair.

In one aspect of this process of the invention, the group from whicheach of R₁₆, and R₁₇ may be selected can be the group consisting ofalkyl, alkenyl, alkynyl, aryl, phenyl, biphenyl, etc., and substitutedalkyl, alkenyl, alkynyl, aryl, phenyl, biphenyl wherein the substituentsare selected from the group of alkyl, alkenyl, alkynyl, aryl, halide,ketone, aldehyde, alcohol, ether, ester, carboxylic acid, primary amino,secondary amino, tertiary amino, amide, nitrile, nitro, epoxide, imine,aziridine, sulfone, phosphone, and silane.

The group from which each of R₁₆, and R₁₇ may be selected, in a narroweraspect of the invention, is the group consisting of alkyl, alkenyl,alkynyl, aryl, and substituted alkyl, alkenyl, alkynyl, aryl, whereinthe substituents are selected from the group of alkyl, aryl, halide,ketone, aldehyde, alcohol ether, ester, carboxylic acid, primary amino,secondary amino, tertiary amino, amide, nitro, epoxide, aziridine,sulfone, phosphone, and silane.

The group from which each of R₁₆, and R₁₇ may be selected can also bethe group consisting of alkyl and aryl, and substituted alkyl and aryl,wherein the substituents are selected from the group of alkyl, aryl,halide, ketone, aldehyde, alcohol, ether, ester, carboxylic acid,primary amino, secondary amino, tertiary amino, amide, nitro, epoxide,aziridine, sulfone, phosphone, and silane.

More preferably, the substituents are selected from the group of halide,ketone, alcohol and ester.

Again, wherein R₅ of compound III can be selected as previouslydescribed.

The compound having formula III preferably has a lower oxidationpotential than that of a compound having formula II, and preferably isoxidized at a faster rate than a compound having formula II under theconditions of electrolysis.

In one general aspect, the invention involves including a carboxylateanion in the anodic cell in which the hydrazine compound II is oxidized.Preferably, the cell is substantially free, or even completely free, ofa toxic metal catalyst. Toxic metal catalysts that are to avoidedinclude of lead cadmium, cerium, cobalt, chromium, copper, ion, mercury,iridium, manganese, molybdenum, nickel, osmium, palladium, rhenium,rhodium, ruthenium, antimony, thallium, tin and vanadium.

The anodic electrode is preferably a platinum electrode.

In a preferred aspect, the acid form of the carboxylate has a firstpK_(a), and the anolyte solution further includes an acid having asecond pK_(a) wherein the second pK_(a) exceeds the first pK_(a).

Preferably, the carboxylate and the acid having the second p& aresolubilized in the solution and the carboxylate is provided in solutionin a stoichiometric amount equal to at least half that of the hydrazinederivative, but more preferably to at least 60% that of the hydrazinederivative, or at least 70% that of the hydrazine derivative, or 80%that of the hydrazine derivative, or 90% that of the hydrazinederivative, or the carboxylate can be present in a stoichiometric amountabout equal to that of the hydrazine derivative, or it could be said, inan amount at least as great as that of the hydrazine derivative.

Usually, the acid form of the carboxylate has the formula RCO₂H whereinR is an organic group. According to a preferred aspect, the acid for ofthe carboxylate has the formula RCO₂H wherein R is an alkyl group or ahaloalkyl group.

The first pK_(a) is preferably in the range of about −2 to about +7,more preferably in the range of about −1 to about +6, more preferably inthe range of about 0 to about +5. The first pK_(a) can be about 0.3first pK_(a), or it can be about 2.8, or the first pK_(a) can be about4.8. The carboxylate can be one or more of acetate, trifluoroacetate,and monochloroacetate.

The acid is preferably an ammonium acid and the second pK_(a) preferablyexceeds the first pK_(a) by at least 2. The ammonium acid typically hasthe wherein each of R₁, R₂ and R₃ is an organic group or hydrogen.Commonly, each of R₁, R₂ and R₃ of the ammonium acid is an alkyl group(e.g., methyl, ethyl, propyl, butyl and pentyl) or hydrogen. In aspecifically disclosed aspect of the invention, the acid having thesecond pK_(a) is triethylammonium.

In another aspect, the anolyte solution includes a counterion to thecarboxylate, the counterion having the formula R₁R₂R₃ R₄ N⁺ wherein eachof R₁, R₂, R₃, and R₄ is an organic group selected from the groupdescribed in connection with R₁, R₂ and R₃ of R₁R₂R₃NH⁺.

The contacting step is preferably carried out in an anodic half celldivided from and operatively linked to a cathodic half cell. Preferably,the half cells are linked by an ion permselective diaphragm. Thediaphragm is preferably made up of a synthetic polymer having anionsaffixed (usually covalently bonded) thereto. A preferred anion isperfluorosulfonate. A commercially available diaphragm suitable for manyaspects of the invention is that sold under the name Nafion.

In one aspect of the invention, compound II, V, or VII, as the case maybe, has a more positive potential than the voltage at which thecontacting step is conducted.

Compound III preferably has first and second peak potentials, each ofwhich potentials is between about 0 and 3 volts against Ag/AgCl, morepreferably between about 1 and 2 volts.

Preferably, the mole ratio of the compound having formula III to thecompound having formula II, V, or VII, as the case may be, is from about1:1 to about 1000:1; more preferably between 500:1 and 1:1; morepreferably between about 100: and 1:1; more preferably between about25:1 and 1:1; more preferably between about 10:1 and 1:1; morepreferably between about 5:1 and 1:1, more preferably between about 2:1and 1:1.

The process can be carried out such that the electric potential appliedduring the contacting step is applied for a period between about 1minute and 10 hours.

In another aspect the invention is a process of addition of a nitrogenacross a multiple bond of an organic molecule wherein a first atom ofthe multiple bond is a carbon atom, and the second atom is selected fromthe group of carbon, oxygen and nitrogen, the improvement comprisingelectrochemically generating the nitrogen for the addition from aprimary hydrazine derivative in the presence of a carboxylate anion. Itis preferred here that the nitrogen is generated from a compound havingthe structure indicated by formula III, as defined above and that theorganic molecule has the structure indicated by formula I formula VII.

Another process of the invention is addition of a nitrogen to aheteroatom of an organic molecule wherein the heteroatom forms a doublebond with an oxygen atom and is a P, S, Se or Te atom, the improvementcomprising electrochemically generating the nitrogen for the additionfrom a primary hydrazine derivative in the presence of a carboxylateanion. Again, the nitrogen is preferably generated from a compoundhaving the structure indicated by formula III, as defined above and theorganic molecule has the structure indicated by formula V.

Another aspect of the invention is a process for electrochemicallygenerating a nitrene. The process includes exposing a hydrazinederivative contained in an anolyte solution of an electroytic cell tothe anode of the cell in the presence of a carboxylate ion, wherein oneof the nitrogens of the hydrazine group is a primary amino group.

Preferably, the anolyte solution is substantially free of a metalcatalyst, particularly a toxic metal catalyst.

Preferably, the anode a platinum electrode.

Preferably, an acid form of the carboxylate has a first pK_(a), and theanolyte solution further comprises an acid having a second pK_(a)wherein the second pK_(a) exceeds the first pK_(a), and the carboxylateand acid (or counterion to the carboxylate) are selected as describedabove.

Preferably, the carboxylate and the acid having the second pK_(a) aresolubilized in the solution and the carboxylate is provided in solutionin a stoichiometric amount equal to at least half that of the hydrazinederivative, but more preferably to at least 60% that of the hydrazinederivative, or at least 70% that of the hydrazine derivative, or 80%that of the hydrazine derivative, or 90% that of the hydrazinederivative, or the carboxylate can be present in a stoichiometric amountabout equal to that of the hydrazine derivative, or it could be said, inan amount at least as great as that of the hydrazine derivative.

In this process for generating a nitrene, the hydrazine derivative canbe a molecule having the structure indicated as formula III as describedabove, and the anolyte solution can be a solvent as described above.

In another aspect, the invention is an apparatus for electrochemicalgeneration of a nitrene. The apparatus includes an anodic half celloperatively linked to a cathodic half cell, and an anolyte solutioncomprising a carboxylate anion and a primary hydrazine derivative.

Preferably, the half cells are linked by an ion permselective diaphragm.A preferred diaphragm is a synthetic polymer having anions affixedthereto, as by covalent bonding, and the anions can includeperfluorosulfonate groups. A commercially available diaphragm suitablefor use according to many processes of the invention is a Nafionmembrane.

The hydrazine of the apparatus includes any of those having formula III,as described above.

Preferably, the anolyte solution is substantially free of a metalcatalyst

Preferably, the anode of the apparatus is a platinum electrode.

Preferably, the an acid form of the carboxylate of the apparatus has afirst pK_(a), and the anolyte solution includes an acid having a secondpK_(a) wherein the second pK_(a) exceeds the first pK_(a). Thecarboxylate and counterion included in the apparatus can be selected andincluded in the apparatus as described above.

An apparatus of the invention can be used for nitrene generation, anaziridination, sulfoximation, or other nitrogen addition to a suitableorganic substrate.

Another aspect of the invention is a process for screening an olefin forelectrochemical aziridination of an olefin with a hydrazine derivative,the process comprising the steps of:

-   -   providing the olefin;    -   determining the redox potential of the olefin at a predetermined        voltage at which the aziridine derivative is oxidized, wherein a        said olefin determined to have a less positive potential than        the predetermined voltage is eliminated as a candidate for        electrochemical aziridination by the hydrazine derivative.

In another aspect, the invention is a process for screening an olefinfor electrochemical aziridination of an olefin with a hydrazinederivative, the process comprising the steps of:

-   -   providing the olefin;    -   determining the redox potential of the olefin at a predetermined        voltage at which the aziridine derivative is oxidized, wherein a        said olefin determined to have a more positive potential than        the predetermined voltage is selected as a candidate for        electrochemical aziridination by the hydrazine derivative.

Preferably, the hydrazine derivative has first and second peakpotentials, each of which potentials is between about 0 and 3 voltsagainst Ag/AgCl, more preferably between about 1 and 2 volts.

BRIEF DESCRIPTION OF THE DRAWINGS

Reference is made to the attached drawings, in which:

FIG. 1 shows cyclic voltammetry (CV) of N-aminophthalimide (dashed line)and cyclohexene (solid line) in acetonitrile with 0.1 M HEt₃NOAc onplatinum electrode; y-axis: current, 10⁻⁶ A, x-axis: potential vsAg/AgCl, V;

FIG. 2 shows Scheme 1, electrochemical aziridination of olefins;

FIG. 3 shows five olefins which did not undergo electrochemicalaziridination;

FIG. 4 shows cyclic voltammetry of N-aminophthalimide (dashed line) andcyclohexene (solid line) in acetonitrile with 0.1 M HEt₃NOAc on glassycarbon electrode; y-axis: current, 10⁻⁶ A, x-axis: potential vs Ag/AgCl,V;

FIG. 5 shows cyclic voltammetry of N-aminophthalimide (dashed line) andtetramethylene sulfoxide (solid line) in acetonitrile with 0.1 MHEt₃NOAc on platinum electrode; y-axis: current, 10⁻⁶ A, x-axis:potential vs Ag/AgCl, V;

FIG. 6 shows cyclic voltammetry of N-aminophthalimide (dashed line) andtetramethylene sulfoxide (solid line) in acetonitrile with 0.1 MHEt₃NOAc on glassy carbon electrode; y-axis: current, 10⁻⁶ A, x-axis:potential vs Ag/AgCl, V;

FIG. 7 shows Scheme 2, electrochemical sulfoximination;

FIG. 8 shows Scheme 3, a proposed mechanism for Pb(OAc)₄-mediatedaziridination; and

FIG. 9 shows Scheme 4, a proposed mechanism for electrochemicaloxidation of N-aminophthalimide.

DESCRIPTION OF PREFERRED EMBODIMENTS

General Information

Cyclohexene, 2-cyclohexen-1-one, 2-methyl-2-pentene,3-bromo-2-methyl-1-propene, methyl trans-cinnamate, cyclooctene,isoprene, trans-chalcone, 4-hexen-3-one, dimethyl fumarate, dimethylmaleate, cinnamyl alcohol, hydrazine monohydrate, phthalimide, cis- andtrans-1,2-dichlorobutene, methyl p-tolyl sulfoxide, phenyl sulfoxide,phenyl vinyl sulfoxide, tetramethylene sulfoxide, benzyl phenyl sulfide,thiophenol, acrylonitrile, tetrabutylammonium hydroxide,3-chloroperoxybenzoic acid (mCPBA), anisole, sodium benzenesulfinate,thionyl chloride, benzoylchloride, and triethylamine were purchased fromAldrich Chemical Company. DMSO was purchased from BDH Inc., Canada.Anhydrous aluminum chloride was purchased from Anachemia Canada Inc.Column chromatography was carried out using 230-400 mesh silica gel. ¹HNMR spectra were referenced to residual CHCl₃ (δ 7.26 ppm) and ¹³Cspectra were referenced to CDCl₃ (δ 77.2 ppm). Cyclic voltammetrycharacterization was conducted on a BAS CV-50W Voltammetric Analyzer(Bioanalytical Systems, Inc.) equipped with a BAS C3 three-electrodecell stand. A three-compartment (anodic: 2.0 cm dia.×10 cm; cathodic:2.0 cm dia.×10 cm; reference: 1.0 cm dia×7 cm) divided cell with glassfrit (medium pore size) separators was used for electrochemicalaziridination of olefins and imination of sulfoxides. HPLC analysis wasperformed on a Hewlett Packard Series 1100 HPLC system with a DaicelChiralcel AS column.

N-aminophthalimide⁷: Hydrazine monohydrate (4.4 g) in 95% ethanol (80mL) was treated with powdered phthalimide (12 g) and the mixture wasstirred at room temperature for 2 min. The resulting spongy mass wasquickly heated and refluxed for 3 min. while ammonia was evolved. Coldwater (250 mL) was added at once and N-aminophthalimide crystallizedduring an hour. Recrystallization from 95% ethanol gave white needles(5.6 g, 43%, Mp 223-224° C.).

Electrochemical Aziridination of Cyclohexene

The anodic compartment was charged with 82 mg (1.0 mmol) cyclohexene,210 mg (1.3 mmol) N-aminophthalimide, 60 mg (1.0 mmol) acetic acid(glacial), 101 mg (1.0 mmol) triethylamine, and 20 mL acetonitrile.Portions of 0.05 M AcOH in MeCN were added to the cathodic (20 mL) andreference (4 mL) compartments. Platinum foils (2.5×2.5 cm, 99.99%) wereused as working and auxiliary electrodes. Silver wire (1.5 mm dia.,99.99%) was used as a pseudo-reference electrode. The electrolysis wasperformed at +1.80 V (with an AMEL potentiostat, Model 2049) at ambienttemperature and was stopped when the cell current dropped to less than5% of its original value. The contents of anodic compartment werecollected and concentrated in vacuo. The residue was washed with waterand extracted with dichloromethane (3×5 mL). The organic phases werecombined, dried over MgSO₄, concentrated, charged onto a silica gelcolumn, and eluted using EtOAc/hexane (1:3) which afforded7-phthalimido-7-azabicyclo[4.1.0]heptane (1) as a yellow solid (223 mg,85%).

Electrochemical aziridination of each of the olefin substrates listed inTable 1 was carried out, and products isolated, under similarconditions, except that for the aziridination of isoprene, which wascarried out at 0° C. to avoid evaporation of isoprene.

The compounds were characterized as indicated below.

7-Phthalimido-7-azabicyclo[4.1.0]heptane (1): ¹H NMR (CDCl₃) δ:7.24-7.75 (m, 4H), 2.72-2.75 (m, 2H), 2.20-2.30 (m, 2H), 1.90-2.10 (m,2H), 1.20-1.50 (m, 4H). Mp 132-133° C. (lit.⁸ 133-136° C.).

7-Phthalimido-7-aiabicyclo[4.1.0]heptan-2-one (2): ¹H NMR (CDCl₃) δ:7.60-7.90 (m, 4H), 3.42-3.46 (m, 1H), 3.07 (d, 1H, J=7.2 Hz), 2.49-2.56(m, 2H), 1.60-2.15 (m, 4H). ¹³C NMR (CDCl₃) δ: 202.91, 164.31, 134.00,129.90, 122.98, 48.86, 45.97, 36.77, 21.78, 18.03. HRMS 256.0841 (Calc.256.0848 for C₁₄H₁₂N₂O₃). Mp 75-77° C.

1-Phthalimido-2-ethyl-3,3-dimethylaziridine (3): ¹H NMR (CDCl₃) δ:7.64-7.76 (m, 4H), 2.74 (t, 2H, J=7.0 Hz), 1.78-1.90 (m, 1H), 1.48-1.61(m, 1H), 1.39 (s, 3H), 1.27 (s, 3H), 1.14 (t, 1H, J=7.3 Hz). ¹³C NMR(CDCl₃) δ: 166.35, 134.01, 130.90, 122.95, 54.38, 47.92, 22.10, 21.07,19.22, 11.50. HRMS 244.1209 (Calc. 244.1212 for C₁₄H₁₆N₂O₂).

1-Phthalimido-2-bromomethyl-2-methylaziridine (4): ¹H NMR (CDCl₃) δ:7.65-7.85 (m, 4H), 3.77 (dd, 0.78H, J=10.5, 1.0 Hz), 3.73 (dd, 0.22H,J=10.5, 1.8 Hz), 3.27 (d, 0.78H, J=10.5 Hz), 3.17 (d, 0.22H, J=10.5 Hz),2.93 (dd, 0.78H, J=1.0, 3.0 Hz), 2.89 (d, 0.22H, J=2.7 Hz), 2.64 (m,0.22H), 2.61 (d, 0.78H, J=3.0 Hz). ¹³C NMR (CDCl₃) δ: 165.95, 134.45,134.36, 130.62, 123.39, 123.31, 46.25, 43.20, 39.24, 15.97. HRMS294.0018 (Calc. 294.0004 for C₁₂H₁₁BrN₂O₂). Mp 81-82° C.

1-Phthalimido-3-phenyl-2-aziridine carboxylic acid methyl ester (5): ¹HNMR (CDCl₃) δ: 7.60-7.80 (m, 4H), 7.30-7.50 (m, 5H), 4.37 (d, 1H, J=5.1Hz), 3.72 (s, 3H), 3.51 (d, 1H, J=5.1 Hz). ¹³C NMR (CDCl₃) δ: 166.73,164.65, 134.48, 134.08, 130.19, 128.66, 127.25, 123.13, 52.96, 49.66,45.96. Mp 141-142° C. (lit.⁹ 144° C.).

9-Phthalimido-9-azabicyclo[6.1.0]nonane (6): ¹H NMR (CDCl₃) δ: 7.65-7.80(m, 4H), 2.52-2.56 (m, 4H), 1.20-1.80 (m, 10H). ¹³C NMR (CDCl₃) δ:165.19, 133.96, 130.60, 122.91, 48.05, 26.54, 26.47, 25.45. Mp 88-89° C.(lit.¹⁰ 89° C.).

1-Phthailmido-2-isopropenylaziridine (7)¹¹: ¹H NMR (CDCl₃) δ: 7.60-7.80(m, 4H), 5.13 (m, 1H), 5.05 (quintet, 1H, J=1.5 Hz), 3.04 (t, 1H, J=6.9Hz), 2.57-2.62 (m, 2H), 1.84 (t, 3H, J=1.5 Hz). ¹³C NMR (CDCl₃)6:165.01, 140.49, 134.08, 130.35, 123.03, 114.83, 46.72, 37.69, 19.26.

1-Phthalimido-2-benzoyl-3-phenylaziridine (8): ¹H NMR (CDCl₃) δ:8.05-8.15 (m, 2H), 7.30-7.80 (m, 12H), 4.69 (d, 1H, J=4.8 Hz), 4.39 (d,1H, J=4.8 Hz). ¹³C NMR (CDCl₃) δ: 190.39, 164.50, 137.25, 135.15,133.95, 133.59, 130.19, 128.74, 128.73, 128.66, 128.57, 127.20, 123.10,50.73, 48.77. Mp 121-123° C. (lit.¹² 124° C.).

1-Phthalimido-2-methyl-3-propionylaziridine (9): ¹H NMR (CDCl₃) δ:7.55-7.80 (m, 4H), 3.38 (quintet, 0.83H, J=5.7 Hz), 3.31 (d, 0.17H,J=5.4 Hz), 3.22 (d, 0.85H, J=5.1 Hz), 2.95-3.12 (m, 1H), 2.63-2.76 (m,1.17H), 1.50 (d, 0.83H, J=5.7 Hz), 1.42 (d, 0.17H, J=5.4 Hz), 1.13 (t,0.17H, J=7.2 Hz), 1.04 (t, 0.83H, J=7.2 Hz). ¹³C NMR (CDCl₃) δ: 202.33,164.91, 134.36, 133.98, 130.35, 123.32, 123.07, 49.88, 45.22, 37.94,16.81, 7.81. HRMS 258.0994 (Calc. 258.1004 for C₁₄H₁₄N₂O₃). Mp102-103.5° C.

trans-1-Phthalimido-2,3-aziridine dicarboxylic acid dimethyl ester(10)¹³: ¹H NMR (CDCl₃) δ: 7.65-7.80 (m, 4H), 3.97 (d, 1H, J=4.8 Hz),3.87 (s, 3H), 3.75 (s, 3H), 3.61 (d, 1H, J=4.8 Hz). ¹³C NMR (CDCl₃) δ:166.60, 165.34, 164.10, 134.34, 130.05, 123.49, 53.56, 53.41, 44.94,42.94. Mp 149-150° C. X-ray data for 10 (recrystallized fromchloroform/hexane): C₁₄H₁₂N₂O₆, MW=304.26, pale yellow prismaticcrystal, crystal size 0.35×0.34×0.25 mm³, orthorhombic, space groupPbca, a=7.3819(2) A, b=16.9618(7) Å, c=22.3703(8) Å, V=2800.99(17) Å³,Z=8, d_(calc)=1.443 g/cm³, F(000)=1264, μ=0.115 mm⁻¹, T=150(1) K, 13499reflections collected, 2447 independent reflections, R=0.0435,R_(w)=0.1021, GOF on F²=1.020.

1-Phthalimido-2-hydroxymethyl-3-phenylaziridine (11): ¹H NMR (CDCl₃) δ:7.15-7.45 (m, 5H), 7.65-7.80 (m, 4H), 4.15-4.35 (m, 1H), 4.02-4.10 (m,0.36H), 3.80-3.90 (m, 0.64H), 3.40-3.60 (m, 1.36H), 3.18-3.22 (m,0.64H), 2.57 (t, 0.36H, J=6.0 Hz), 2.69 (bs, 0.64H). ¹³C NMR (CDCl₃) δ:166.63, 135.82, 134.59, 134.04, 130.49, 129.51, 128.85, 128.67, 128.29,128.25, 127.30, 123.51, 123.03, 62.31, 59.30, 52.42, 48.96, 46.65,46.29. HRMS 294.1000 (Calc. 294.1004 for Cl₇H₁₄N₂O₃). Mp 141-142° C.

1-Phthalimido-2-phenyl-3-aziridine acetic acid methyl ester (12): ¹H NMR(CDCl₃) δ: 7.20-7.80 (m, 9H), 4.34 (dd, 0.47H, J=1.6, 5.6 Hz), 3.89 (d,0.53H, J=5.6 Hz), 3.76 (s, 1.41H), 3;71 (s, 1.59H), 3.66 (d, 0.47H,J=1.6 Hz), 3.05-3.23 (m, 1.53H), 2.50-2.70 (m, 1H). ¹³C NMR (CDCl₃) δ:170.85, 170.73, 166.13, 136.35, 135.26, 134.44, 134.03, 130.99, 130.60,129.71, 128.87, 128.63, 128.27, 128.17, 127.41, 124.58, 123.32, 122.98,52.32, 52.17, 51.56, 48.40, 45.53, 41.05, 37.49, 33.36. HRMS 336.1097(Calc. 336.1110 for Cl₉H₁₆N₂O₄). Mp 113-115° C.

1-Phthalimido-2-phenylacetoxymethyl-2-aziridine carboxylic acid methylester (13, mixture of two diastereomers): ¹H NMR (CDCl₃) δ: 7.55-7.75(m, 4H), 7.20-7.45 (m, 5H), 3.66 (s, 1H), 3.54-3.56 (m, 2.33H), 3.48 (d,0.67H, J=1.8 Hz), 2.95 (d, 0.67H, J=1.8 Hz), 2.83 (d, 0.33H, J=2.1 Hz),2.15 (s, 1H), 2.10 (s, 2H). ¹³C NMR (CDCl₃) δ: 169.28, 169.19, 166.44,166.18, 164.46, 164.31, 136.55, 135.42, 134.15, 134.00, 130.21, 130.09,128.70, 128.36, 128.25, 128.20, 127.83, 127.65, 123.45, 123.02, 72.83,70.80, 53.37, 53.16, 48.69, 39.57, 38.68, 21.15. HRMS 394.1151 (Calc.394.1165 for C₂₁H₁₈N₂O₆).

1-Phthalimido-2-phenylhydroxymethyl-2-aziridine carboxylic acid methylester (14, mixture of two diastereomers): ¹H NMR (CDCl₃) δ: 7.60-7.80(m, 4H), 7.20-7.45 (m, 5H), 5.70 (s, 0.82H), 5.16 (s, 0.181H), 3.80 (b,1H), 3.64 (d, 0.181H, J=2.1 Hz), 3.61 (s, 2.46H), 3.58 (d, 0.82H, J=1.8Hz), 3.55 (s, 0.541), 2.91 (d, 0.18H, J=2.1 Hz), 2.85 (d, 0.82H, J=1.8Hz). ¹³C NMR (CDCl₃) 8:167.01, 165.05, 139.24, 134.34, 130.21, 128.55,128.51, 128.37, 127.94, 127.71, 126.81, 126.73, 123.69, 123.37, 73.37,70.11, 53.26, 52.06, 50.98, 40.19. HRMS 352.1062 (Calc. 352.1059 forCl₉H₁₆N₂O₅).

trans-1-Phthalimido-2,3-bis(chloromethyl)aziridine (15a): ¹H NMR (CDCl₃)δ: 7.60-7.80 (m, 4H), 4.08 (dd, 2H, J=6.0, 11.7 Hz), 3.54 (dd, 2H,J=8.1, 11.7 Hz), 3.20-3.25 (m, 2H). ¹³CNMR (CDCl₃) δ: 164.75, 134.57,130.22, 123.52, 48.05, 40.14.

cis-1-Phthalimido-2,3-bis(chloromethyl)aziridine (15b): ¹H NMR (CDCl₃)δ: 7.60-7.80 (m, 4H), 4.00-4.06 (m, 2H), 3.45-3.60 (m, 3H), 2.98 (dt,1H, J=5.1, 7.5 Hz). ¹³C NMR (CDCl₃) δ: 165.85, 134.62, 130.48, 123.56,47.03, 46.48, 43.50, 40.67.

1-Phthalimido-2-phenyltosylaminomethyl-2-aziridine carboxylic acidmethyl ester (16): ¹H NMR (CDCl₃) δ: 7.65-7.80 (m, 4H), 7.63 (d, 2H,J=12.5 Hz), 7.38 (d, 1H, J=8.2 Hz), 7.18 (bs, 5H), 7.13 (d, 2H, J=12.5Hz), 5.49 (d, 1H, J=8.2 Hz), 3.50 (s, 3H), 3.48 (d, 1H, J=3.1 Hz), 2.35(s, 3H), 2.12 (d, 1H, J=3.1 Hz). ¹³C NMR (CDCl₃) δ: 166.82, 165.43,142.58, 138.93, 136.34, 134.48, 130.14, 129.21, 128.37, 128.29, 128.11,127.26, 123.56, 56.56, 53.44, 49.09, 41.91, 21.55. X-ray data for 16(recrystallized from chloroform/hexane): C₂₆H₂₃N₃O₆S, MW=505.53,colorless prismatic crystal, crystal size 0.29×0.28×0.28 mm³, triclinic,space group P1, a=7.9575(1) Å, α87.6210(10)°, b=8.8478(1) Å,β=79.6990(10)°, c=17.3936(3) Å, γ=73.6590(10)°, V=1156.16(3) Å³, Z=2,d_(calc)=1.452 g/cm³, F(000)=528, μ=0.190 mm⁻¹, T=150(1) K, 13257reflections collected, 5282 independent reflections, R=0.0448,R_(w)=0.0949, GOF on F²=1.045.

Sulfoxide Syntheses

2-Cyanoethyl phenyl sulfoxide: A modified literature procedure¹⁴ wasused to make this compound. Thiophenol (1.10 g, 10 mmol) was addeddropwise to a mixture of acrylonitrile (1.06 g, 20 mmol) andtetrabutylammonium hydroxide (40 wt % aq. 0.1 mL) dissolved indichloromethane (50 mL). The reaction mixture was stirred at roomtemperature for 2 hours and concentrated in vacuo. The residue wascharged onto a silica gel column and eluted with EtOAc/hexane to afford2-cyanoethyl phenyl sulfide (1.50 g, 92%) as a colorless oil. ¹H NMR(CDCl₃) δ: 2.59 (t, 2H, J=7.2 Hz), 3.13 (t, 2H, J=7.2 Hz), 7.30-7.45 (m,5H). ¹³C NMR (CDCl₃) δ: 18.59, 30.58, 127.68, 129.32, 131.37, 133.10.The sulfide (815 mg, 5 mmol) was dissolved in 20 mL DCM and mCPBA(57-86%, 2 g) was added. The reaction mixture was stirred at roomtemperature for 5 hours and concentrated in vacuo. The residue waswashed with saturated aqueous NaHCO₃ and extracted with DCM (3×10 mL).The organic phases were combined, dried over MgSO₄, concentrated, andcharged onto a silica gel column, which was eluted with EtOAc/hexane.2-Cyanoethyl phenyl sulfoxide was obtained as a white solid (770 mg,86%). ¹H NMR (CDCl₃) δ: 2.40-2.60 (m, 11), 2.80-3.00 (m, 2H), 3.10-3.30(m, 1H), 7.40-7.60 (m, 5H). ¹³CNMR (CDCl₃) δ: 9.95, 50.48, 123.89,129.59, 131.72, 141.22. Mp 61-62° C. (lit.¹⁵ 64-65° C.).

4-Methoxydiphenyl sulfoxide: A modified literature procedure¹⁶ was usedto prepare this compound. To a well stirred suspension of sodiumbenzenesulfinate (5.41 g, 30 mmol, dried at 100° C. for 2 h.) in cold(ice water bath) dry toluene (30 mL) was added dropwise thionyl chloride(2.98 g, 25 mmol). The reaction mixture was allowed to warm up to roomtemperature and stirred overnight. Toluene was removed by applying highvacuum (0.5 mmHg) and crude bezenesulfinyl chloride was dissolved in dryDCM (20 mL), cooled to 0-5° C., and was added dropwise to a mixture ofanisole (3.24 g, 30 mmol) and anhydrous aluminum chloride (4.0 g, 30mmol) in DCM (20 mL) at 0-5° C. under nitrogen. This mixture was stirredat 0-5° C. for 3 hours. Water was added slowly and organic phaseseparated, dried over MgSO₄, filtered and concentrated in vacuo to givea pale yellow oil. A hexane wash of the crude material afforded thesulfoxide as a white solid (4.76 g, 82%). ¹H NMR (CMCl₃) δ: 3.81 (s,3H), 6.95 (d, 2H, J=9.0 Hz), 7.40-7.48 (m, 3H), 7.55 (d, 2H, J=9.0 Hz),7.56-7.62 (m, 2H). ¹³C NMR (CDCl₃) δ: 55.74, 114.84, 124.58, 127.21,129.16, 130.69, 136.78, 145.77, 161.88. Mp 85-86° C. (lit.¹⁷ 86-89° C.).

Preparation of (R)-methyl p-tolyl suffoxide¹⁸ and 18: To a solution of(R)-binaphthol (0.10 mmol) in carbon tetrachloride were addedTi(O^(i)Pr)₄ (0.050 mmol) and H₂O (1.0 mmol) under aerial conditions.After the resulting brown solution was stirred at room temperature for 1h, methyl p-tolyl sulfide (1.0 mmol) was introduced by a syringe,followed by TBHP (2.0 mmol, 5.0-6.0 M in decane), and the mixture wasstirred open to air for 7 h. The reaction mixture was directly submittedto column chromatography with silica gel using 1:1 hexane/ethyl acetateas eluent. HPLC analysis on a Daicel Chiralcel AS column (3:7^(i)PrOH/hexane, 1.0 mL/min.) gave 93% ee of the R-enantiomer.Electrochemical sulfoximination of this sample was carried out underabove conditions and HPLC analysis of the product 18 on AS column (3:7iPrOH/hexane, 0.50 ml/min.) gave the ee value of 97%.

Electrochemical Sulfoximination Procedure

For the sulfoxide substrate corresponding to each sulfoximine listed inTable 2, the following procedure was followed. The anodic compartmentwas charged with 1.0 mmol sulfoxide, 210 mg (1.3 mmol)N-aminophthalimide, 78 mg (1.3 mmol) acetic acid (glacial), 130 mg (1.3mmol) triethylamine, and 20 mL acetonitrile. Portions of 0.05 M AcOH inMeCN were added to the cathodic (20 mL) and reference (4 mL)compartments. Platinum foils (2.5×2.5 cm, 99.99%) were used as workingand auxiliary electrodes. Silver wire (1.5 mm dia., 99.99%) was used asa pseudo-reference electrode. The electrolysis was performed at +1.80 Vat ambient temperature and was stopped when the cell current dropped toless than 5% of its original value. The contents of anodic compartmentwere collected and concentrated in vacuo. The residue was washed withwater and extracted with dichloromethane (3×5 mL). The organic phaseswere combined, dried over MgSO₄, concentrated, charged onto a silica gelcolumn, and eluted using EtOAc/hexane to afford sulfoximine. Theisolated products were characterized, as indicated below.

N-Phthalimido-S,S-dimethylsuffoximine (17):¹⁹ ¹H NMR (CDCl₃) δ: 3.29 (s,6H), 7.67-7.71 (m, 2H), 7.79-7.82 (m, 2H). ¹³C No (CDCl₃) δ: 41.39,123.38, 130.74, 134.15, 167.44. Mp 205-206° C. (lit.²⁰ 208-210° C.).

N-Phthalimido-S-methyl-S-Tolyl)sulfoximine (18):²¹ ¹H NMR (CDCl₃) δ:2.43 (s, 3H), 3.33 (s, 3H), 7.35 (d, 2H, J=8.4 Hz), 7.63-7.76 (m, 4H),8.09 (d, 2H, J=8.4 Hz). ¹³C NMR (CDCl₃) δ: 21.90, 42.86, 123.21, 129.61,130.08, 130.80, 133.33, 133.91, 145.49, 167.06. Mp 167-169° C. X-raydata for (R)-18 (recrystallized from toluene): C₁₆H₁₄N₂O₃S, MW=314.35,colorless prismatic crystal, crystal size 0.30×0.12×0.10 mm⁻¹,orthorhombic, space group P2₁/2₁/2₁, a=7.9615(2) Å, b=9.9599(2) Å,c=38.3334(10) Å, V=3039.68(13) Å³, Z=8, d_(calc)=1.374 g/cm³,F(000)=1312, μ=0.227 mm⁻¹, T=150(1) K, 12041 reflections collected, 6335independent reflections, R=0.0614, R_(w)=0.0936, GOF on F²=1.022.

N-Phthallmido-S,S-diphenylsulfoximine (19):²² ¹H NMR (CDCl₃) δ:7.46-7.58 (m, 6H), 7.60-7.62 (m, 2H), 7.72-7.74 (m, 2H), 8.22-8.28 (m,4H). ¹³C NMR (CDCl₃) δ: 123.17, 129.36, 129.59, 130.83, 133.82, 133.85,137.45, 166.81. Mp 218-219° C. (lit. 220-221° C.).

N-Phthalimido-S-phenyl-vinylsulfoximine (20):²² ¹H NMR (CDCl₃) δ: 6.19(dd, 1H, J=0.9, 9.3 Hz), 6.54 (dd, 1H, J=0.9, 16.5 Hz), 6.86 (dd, 1H,J=9.3, 16.5 Hz), 7.50-7.90 (m, 7H), 8.20-8.30 (m, 2H). ¹³C NMR (CDCl₃)6:123.27, 129.50, 1-29.57, 130.86, 131.99, 133.98, 134.39, 135.24,135.93, 167.00. Mp 138-140° C. (lit.²⁰ 136-137° C.).

N-Phthalimido-S-benzyl-S-phenylsulfoximine (21): ¹H NMR (CDCl₃) δ: 4.65(d, 1H, J=20.7), 4.78 (d, 1H, J=20.7), 7.01-7.94 (m, 14H). ¹³C NMR(CDCl₃) S: 61.19, 123.29, 127.19, 128.65, 129.01, 129.18, 130.67,130.98, 131.32, 133.89, 134.01, 134.29, 167.33. HRMS 376.0885 (Calc.376.0882 for C₂₁H₁₆N₂O₃S). Mp 153-155° C.

N-Phthalimido-S-(2-cyanoethyl)S-phenylsulfoximine (22): ¹H NMR (CDCl₃)6:3.01 (t, 2H, J=11.1 Hz), 3.64 (dt, 1H, J=21.5, 11.1 Hz), 3.87 (dt, 1H,J=21.5, 11.1 Hz), 7.64-7.78 (m, 7H), 8.22 (d, 2H, J=11.7 Hz). ¹³C NMR(CDCl₃) S: 12.63, 50.01, 115.90, 123.43, 129.95, 130.11, 130.74, 133.90,134.22, 135.32, 166.98. HRMS 339.0670 (Calc. 339.0678 for C₁₇H₁₃N₃O₃S).

N-Phthalimido-S-(4-methoxyphenyl)S-phenylsulfoximine (23): ¹H NMR(CDCl₃) δ: 3.83 (s, 3H), 6.97 (d, 2H, J=9.3 Hz), 7.48-7.74 (m, 7H),8.17-8.22 (m, 4H). ¹³C NMR (CDCl₃) δ: 55.83, 114.78, 123.22, 127.86,129.27, 129.35, 130.85, 132.02, 133.62, 133.92, 138.07, 164.13, 167.07.HRMS 392.0817 (Calc. 392.0831 for C₂₁H₁₆N₂O₄S).

N-Phthalimidotetramethylene sulfoximine (24): ¹H NMR (CDCl₃) δ:2.33-2.44 (m, 4H), 3.14-3.28 (m, 21′), 3.64-3.78 (m, 2H), 7.60-7.90 (m,4H). ¹³C NMR (CDCl₃) δ: 24.09, 52.90, 123.37, 130.92, 134.16, 167.56. Mp179-180° C. HRMS 264.0567 (Calc. 264.0569 for C₁₂H₁₂N₂O₃S).

Electrochemical Aziridination of Olefins.

Recently, Compton and coworkers²³ showed that an electrochemical redoxcycle involving Pb(IV) and Pb(II) can be realized. The cyclicvoltammetry (CV) of Pb(OAc)₂ in acetonitrile was found to give a valueof +1.60 V (vs. Ag/AgCl) for the oxidation potential of Pb(II) toPb(IV),²³ whereas the CV of N-aminophthalimide (0.01 M in acetonitrile)shows two irreversible one-electron oxidation processes with anodic peakpotentials at +1.35 V and at +1.68 V (vs. Ag/AgCl). Using 10 mol %Pb(OAc)₂, the electrochemical aziridination of cyclohexene withN-aminophthalimide was conducted at a constant potential of +1.60 V, andgave a 75% isolated yield of 1.

Furthermore, the CV of cyclohexene²⁴ (0.01 M in acetonitrile) has beenfound to produce an anodic current of −1.3 μA at +1.68 V (vs Ag/AgCl),which is only a small fraction of the current recorded forN-aminophthalimide (−152 μA, FIG. 1). This indicates that the backgroundoxidation of olefins on a platinum electrode is kinetically disfavoreddue to olefin overpotential. It was found that a simple combination ofplatinum electrodes, triethylamine, and acetic acid leads to a roomtemperature nitrene transfer from N-aminophthalimide to cyclohexene(Scheme 1 of FIG. 2). The reaction utilized only a small excess ofN-aminophthalimide relative to the olefin and can be performed in adivided cell using a silver wire as a pseudo reference electrode.

A variety of olefins were subject of aziridination in this process, assummarized in Table 1. Both electron-rich and electron-poor olefins wereconverted to aziridines electrochemically. For certain monosubstitutedterminal olefins (FIG. 3) the electrochemical aziridination was notfound to be successful although the redox behavior of these olefins issimilar to that of the others. The cis-olefin dimethyl maleate was alsofound to be inert towards electrochemical aziridination, while itstrans-isomer dimethyl fumarate gave excellent yield of aziridine (Table1, entry 10). In all cases with inert olefins, N-aminophthalimide wascompletely converted to phthalimide (precipitated out during thereaction) and the olefins were recovered quantitatively. A possibleexplanation of this observation is that the nitrene transfer to olefinis either very slow, or it might be reversible. In the first casedimerization of the N-acetoxyamino intermediate (Scheme 2 of FIG. 7)predominates to give phthalimide as product. In the latter case theaziridine product could be produced to then quickly decompose to giveback the nitrene intermediate which may also undergo a dimerizationprocess affording the more stable product phthalimide.

The aziridination reaction was found not to take place when a graphiteelectrode was used. The CV study on carbon electrode revealed thatanodic current corresponding to the oxidation cyclohexene (−5.3 μA at+1.68 V) was comparable to that of N-aminophthalimide (−15.6 μA at +1.68V). Such small difference in the rate of electrochemical oxidationapparently does not secure high selectivity in olefin aziridination.

Electrochemical Imination of Sulfoxides

Imination of sulfoxides, to obtain the corresponding sulfoximines, withN-aminophthalimide is known to be mediated by Pb(OAc)₄.²⁵ As mentionedabove, the CV of N-aminophthalimide (0.01 M in acetonitrile) on aplatinum electrode (FIG. 5) shows two irreversible one-electronoxidation processes with anodic peak potentials at +1.35 V and +1.68 V(vs Ag/AgCl). At +1.68 V, tetramethylene sulfoxide (0.01 M inacetonitrile) produces a considerably smaller anodic current of −7.52 μAthan the current observed for N-aminophthalimide (−152 μA), suggesting arelatively kinetically sluggish background oxidation of sulfoxides on aplatinum electrode.

The nature of electrode material was found to be important theelectrochemical transfer process. The CV (FIG. 6) of tetramethylenesulfoxide (0.01 M in acetonitrile) on a glassy carbon electrode showedtwo irreversible oxidation processes with peak potentials at +1.64 V and+1.82 V and a much higher anodic current (−272 μA) than that ofN-aminophthalimide at +1.68 V (−15.6 μA). Thus, bulk electrolysis oftetramethylene sulfoxide in the presence of N-aminophthalimide on agraphite anode gave tetramethylene sulfone as the major product with noevidence of sulfoximine formation.

On the platinum anode, the electrolysis conditions were similar to thoseof aziridination (Scheme 2 of FIG. 7). A small excess ofN-aminophthalimide relative to the sulfoxide was used. The electrolysiswas performed in a divided cell using a silver wire as apseudo-reference electrode, which was calibrated against theferrocene/ferricinium couple in the electrolysis medium (E_(pa)=0.47 V,E_(pc)=0.30 V). No special precautions to exclude moisture or air weretaken. The reaction was stopped when the cell current dropped to lessthan 5% of its original value. Imination of a variety of sulfoxidesubstrates was achieved, as shown in Table 2. For sulfoxide 20 (Table 2,entry 4), no aziridination product was observed, indicating thepossibility to achieve chemoselective nitrene transfer to the sulfoxidemoiety. There was no evidence for the background formation of sulfoneby-product. The oxidative imination of sulfides (resulting insulfimines) was also performed using the same methodology. However, amixture of products consisting mainly of sulfoxide and sulfoximine wasobtained, presumably, due to the less positive oxidation potential ofsulfides compared to N-aminophthalimide.

Furthermore, this electrochemical nitrene transfer process was found tobe stereospecific. An enantiomerically enriched (93% ee of theR-enantiomer)¹⁸ sample of methyl p-tolyl sulfoxide was electrolyzedunder the conditions described above. The ee value measured for theproduct sulfoximine 18 was the same (97%) within the error of HPLCanalysis and the X-ray structure of the product showed retention ofconfiguration, indicating that no racemization occurred during nitrenetransfer process.

Mechanistic Consideration in Electrochemical Aziridination Process

The mechanism of the Pb(OAc)₄ mediated olefin aziridination withN-aminophthalimide and other N-amino heterocycles has been studied byAtkinson and coworkers.²⁶ It has been suggested that the oxidation ofN-aminophthalimide by Pb(OAc)₄ generates an N-acetoxyamino intermediate,which can be isolated or is stable enough to be observed by NMR at lowtemperature (<5° C.). Addition of olefin at higher temperature to thisintermediate results in aziridine (Scheme 3 of FIG. 8). In the absenceof olefin, the N-acetoxyamino intermediate dimerizes to generate thetetrazene which then decomposes to phthalimide by extrusion of N₂.Fuchigami and coworkers²⁷ have shown that the electrochemical oxidationof N-aminophthalimide using Bu₄NBF₄ or LiClO₄ as supporting electrolyteat 0° C. gave tetrazene as major product and 10-20% of phthalimide. Theauthors proposed an electrochemically generated N-nitrene intermediatewhich inserts into the N—H σ-bond of the unoxidized N-aminophthalimideto afford the tetrazane intermediate (Scheme 4 of FIG. 9). The tetrazaneis further oxidized to give tetrazene.

Here, the results obtained in the oxidation of N-aminophthalimide in thepresence of olefin with supporting electrolytes other thantriethylammonium acetate are shown in Table 3. In cases of LiClO₄,Bu₄NBF₄, and Et₄NOTs, no aziridine was detected while phthalimide wasisolated in high yields (80-85%). The apparent need for a carboxylateanion of some sort, particularly acetate, for aziridine generationimplies that a similar N-acetoxyamino intermediate may be involved inthis process. This is also evidenced by the correlation between theaziridine yields and acetate concentrations.

More mechanistic evidence has been obtained by comparing theelectrochemical and chemical (Pb(OAc)₄ mediated) aziridination results,especially in stereochemical aspects. Dreiding and coworkers²⁸ showedthat the Pb(OAc)₄ promoted aziridination is stereospecific, i.e.,E-olefins afford only the trans-aziridines and Z-olefins only thecis-aziridines. Here, the NMR analysis and X-ray structure of 10 showedexclusive formation of a trans-aziridine. The corresponding Z-olefin,dimethyl maleate, was found to give aziridination product, however,electrochemical aziridination of the E- and Z-1,2-dichloro-2-butene andthe results showed that this process is also stereospecific (Table 4,entries 2, 3). Furthermore, the diastereoselectivity of theelectrochemical and chemical approaches were found to be comparable(Table 4, entries 4, 5). An exclusive syn-aziridine (shown by its X-raystructure) was obtained for 16.

The continuum of accessible electrode potentials provided byelectrochemistry enables differentiating substrates based on theiroverpotentials.

All citations referred to in this document are incorporated herein byreference in their entirety, as though the contents of each suchreference was reproduced in its entirety in this document.

The scope of protection sought for any invention described herein isdefined by the claims which follow. It will be appreciated by thoseskilled in the art that a variety of possible combinations andsubcombinations of the various compounds obtainable through theprocesses described herein exist, and all of these combinations andsubcombinations should be considered to be within the inventor'scontemplation though not explicitly enumerated here. This is also trueof the variety of aspects of the processes and the combinations andsubcombinations of elements thereof. TABLE 1 ElectrochemicalAziridination of Olefins. product entry Substrate (yield, %) 1

2

3

4

5

6

7

8

9

10

11

12

13

14

^(a)reaction at 0° C.^(b)2:1 ratio of diastereomers.^(c)4.4:1 ratio of diastereomers.

TABLE 2 Electrochemical Synthesis of N-Phthalimido Sulfoximines.N-phthalimido Entry sulfoximine (yield, %) 1

2

3

4

5

6

7

8

TABLE 3 Cation and Anion Effects on Electrochemical Aziridination with1.0 mmol Cyclohexene, 1.3 mmol N-Aminophthalimide, and x mmol SupportingElectrolyte. amount of supporting X yield of aziridine phthalimideelectrolyte (mmol) (%) (mmol) LiClO₄ 1.0 0 1.06 Bu₄NBF₄ 1.0 0 1.11Et₄NOTs 1.0 0 1.03 1:1 Et₃N/CF₃CO₂H 1.0 90 0.33 1:1 Et₃N/ClCH₂CO₂H 1.087 0.33 Me₄NOAc 1.0 85 0.39 Et₄NOAc 1.0 81 0.37 Bu₄NOAc 1.0 83 0.37 1:1Et₃N/HOAc 0.20 55 0.64 ″ 0.50 69 0.51 ″ 2.0 83 0.40 ″ 5.0 89 0.32

TABLE 4 Comparison of Electrochemical and Chemical Aziridination ofOlefins. configuration of product entry Substrate Productelectrochemical method (yield, %) chemical method^(a) 1

trans^(b) (92) trans 2

trans (76) trans 3

cis (73) cis 4

4.4:1 d.r. (73) 4.2:1 d.r. 3.8:1 d.r.^(c) 5

syn^(b) (78) syn^(a)All aziridination reactions with Pb(OAc)₄ were studied by NMR inCD₃CN. The products were not isolated and their configurations weredetermined by comparing with the products from electrochemicalreactions.^(b)X-ray structure.^(c)NMR study in CDCl₃.

REFERENCES

-   ¹ McCoull, W.; Davis, F. A. Synthesis 2000, 10, 1347.-   ²Skancke, A.; van Vechten, D.; Liebman, J. F.; Skancke, P. N. J.    Mol. Struct. 1996, 376, 461.-   ³ Kolb, H. C.; Finn, M. G.; Sharpless, K. B. Angew. Chem. Int. Ed.    2001, 40, 2004.-   ⁴(a) Muller, P. Adv. Catal. Processes 1997, 2, 113. (b) Li, Z.;    Conser, K. R.; Jacobsen, E. N. J. Am. Chem. Soc. 1993,    115, 5326. (c) Evans, D. A.; Bilodeau, M. T.; Faul, M. M. J. Am.    Chem. Soc. 1994, 116, 2742. (d) Noda, K; Hosoya, N.; Irie, R.; Ito,    Y.; Katsuki, T. Synlett 1993, 7,469. (e) Muller, P.; Baud, C.;    Jacquier, Y. Tetrahedron 1996, 52, 1543. (f) Jeon, H. J.;    Nguyen, S. T. Chem. Commun. 2001, 235.-   ⁵ Atkinson, R. S. in Azides and Nitrenes; Scriven, E. F. V. Ed.,    Academic Press: Orlando, 1984 and references cited therein.-   ⁶ Daland, R. J. Lead and Human Health: An Update; American Council    on Science and Health: New York, 2000 and references cited therein.-   ⁷ Drew, H. D. K.; Hatt, H. H. J. Chem. Soc. 1937, 16.-   ⁸ Anderson, A. G.; Fagerburg, D. R.; Tetrahedron 1973, 29, 2973.-   ⁹ Person, H.; Tonnard, F.; Foucaud, A.; Fayat, C. Tetrahedron Lett.    1973, 27, 2495. Hoesch, L.; Egger, N.; Dreiding, A. S. Helv. Chim.    Acta 1978, 61, 795.-   ¹¹ Atkinson, R. S.; Malpass, J. R. J. Chem. Soc. Perkin Trans. I    1977, 2242.-   ¹² Person, H.; Fayat, C.; Tonnard, F.; Foucaud, A. Bull. Soc. Chim.    Fr. 1974, 635.-   ¹³ Gilchrist, T. L.; Anderson, D. J. J. Chem. Soc. C 1971, 12, 2273.-   ¹⁴ Krishnan, G.; Sampson, P. Tetrahedron Lett. 1990, 31, 5609.-   ¹⁵ Yoshimura, T.; Yoshizawa, M., Tsukurimichi, E. Bull. Chem. Soc.    Jpn. 1987, 60, 2491.-   ¹⁶ Chasar, D. W.; Pratt, T. M. Phosphorus Sulfur 1978, 5, 35.-   ¹⁷ Chasar, D. W.; Pratt, T. M. Shockcor, J. P. Phosphonts Sulfr    1980, 8, 183.-   ¹⁸ For preparation of enantiomerically enriched sulfoxide, see:    Komatsu, N.; Hashizume, M.; Sugita, T.; Uemura, S. J. Org. Chem.    1993, 58, 4529.-   ¹⁹ Back, T. G.; Kerr, R. G. Can. J. Chem. 1982, 60, 2711.-   ²⁰ Anderson, D. J.; Horwell, D. C.; Stanton, E. J. Chem. Soc. Perkin    11972, 1317.-   ²¹ Annunziata, R; Barbarella, G. Org. Magn. Reson. 1984, 22, 250.-   ²² Annunziata, R.; Cinquini, M. J. Chem. Soc. Perkin I 1979, 1684.-   ²³ Marken, F.; Leslie, W. M.; Compton, R. G.; Moloney, M. G.;    Sanders, E.; Davies, S. G.; Bull, S. D. J. Electroanal. Chem. 1997,    424, 25.-   ²⁴ For CV Data on various olefins, see: Tsuchiya, M.; Akaba, R.;    Aihara, S.; Sakuragi, H.; Tokumaru, K. Chem. Lett. 1986, 1727.-   ²⁵ (a) Ohashi, T.; Masunaga, K.; Okahara, M.; Komori, S. Synthesis    1971,96. (b) Colonna, S.; Stirling, C. J. M. J. Chem. Soc., Perkin    Trans. I 1974, 2120. (c) Kim, M.; White, J. D. J. Am. Chem. Soc.    1977, 99, 1172. (d) Kemp, J. E. G.; Closier, M. D.; Stefanich, M. H.    Tetrahedron Lett. 1979, 3785.-   ²⁶ Atkinson, R. S.; Grimnshire, M. J.; Kelly, B. J. Tetrahedron    1989, 45, 2875.-   ²⁷ Fuchigami, T.; Sato, T.; Nonaka, T. Electrochem. Acta 1986, 31,    365.-   ²⁸ Chilmonczyk, Z.; Egli, M.; Behringer, C.; Dreiding, A. S. Helv.    Chim. Acta 1989, 72, 1095.

1. An electrochemical process for the formation of a compound havingformula I,

the process comprising step of: contacting a compound having formula IIand a compound having formula III,

with each other in an electrolytic cell under conditions of electrolysissufficient to form the compound of formula I, wherein: (A) A is selectedfrom the group consisting of C, N and O, and (i) when A is a carbonatom, each of R₁, R₂, R₃, and R₄ is hydrogen or an organic group; (ii)when A is a nitrogen atom, each of R₁, R₂, and R₃, is hydrogen or anorganic group, and R₄ is an electron pair; (iii) when A is an oxygenatom, each of R₁ and R₂ is hydrogen or an organic group, and each of R₃and R₄ is an electron pair; and (iv) R₅ is NR₆R₇ and each of R₆ and R₇is an organic group.
 2. The process of claim 1, wherein A is a carbonatom.
 3. The process of claim 1, wherein A is a nitrogen atom.
 4. Theprocess of claim 1, wherein A is an oxygen atom.
 5. The process of claim2, 3, or 4, wherein the group of organic groups from which each of R₁,R₂, R₃, and R₄ may be selected is the group consisting of alkyl,alkenyl, alkynyl, aryl, and substituted alkyl, alkenyl, alkynyl, aryl,wherein the substituents are selected from the group of alkyl, alkenyl,alkynyl, aryl, halide, ketone, aldehyde, alcohol, ether, ester,carboxylic acid, primary amino, secondary amino, tertiary amino, amide,nitrile, nitro, epoxide, imine, aziridine, sulfone, phosphone, andsilane.
 6. The process of claim 5, wherein said group from which each ofR₁, R₂, R₃, and R₄ may be selected is the group consisting of alkyl,alkenyl, alkynyl, aryl, and substituted alkyl, alkenyl, alkynyl, aryl,wherein the substituents are selected from the group of alkyl, aryl,halide, ketone, aldehyde, alcohol, ether, ester, carboxylic acid,primary amino, secondary amino, tertiary amino, amide, nitro, epoxide,aziridine, sulfone, phosphone, and silane.
 7. The process of claim 6,wherein said group from which each of R₁, R₂, R₃, and R₄ may be selectedis the group consisting of alkyl and aryl, and substituted alkyl andaryl, wherein the substituents are selected from the group of alkyl,aryl, halide, ketone, aldehyde, alcohol, ether, ester, carboxylic acid,primary amino, secondary amino, tertiary amino, amide, nitro, epoxide,aziridine, sulfone, phosphone, and silane, and preferably wherein eachof R₁, R₂, R₃, and R₄ includes up to 20 carbon atoms, more preferably upto 18 carbon atoms, more preferably up to 16 carbon atoms, morepreferably up to 14 carbon atoms, or up to 12 carbon atoms, or up to 10carbon atoms, or up to 8 carbon atoms, or up to 6 carbon atoms.
 8. Theprocess of claim 5, 6 or 7, wherein the substituents are selected fromthe group of halide, ketone, alcohol and ester.
 9. The process of any ofclaims 2 to 8 wherein, when A is a carbon atom, (i) if R₃ and P4 areeach hydrogen, then each of R₁ and R₂ is not hydrogen, or the doublebond shown in formula II is conjugated with another olefinic doublebond, (ii) if a first carbon atom of the double bond shown in formula IIis in an α-position with respect to a carbonyl group of R₁, then thesecond carbon atom of the double bond is not in an α-position withrespect to a carbonyl group of R₃, and (iii) if a first carbon atom ofthe double bond shown in formula II is in an α-position with respect toa carbonyl group of R₂, then the second carbon atom of the double bondis not in an α-position with respect to carbonyl group of R₄.
 10. Theprocess of any of claims 1 to 9, wherein compound II is selected fromthe group consisting of cyclohexene, cyclohex-2-enone,2-methyl-pent-2-ene, 3-bromo-2-methyl-propene, trans-3-phenyl-acrylicacid methyl ester, cyclooctene, 2-methyl-buta-1,3-diene,trans-1,3-diphenylpropenone, trans-hex-4-en-3-one, trans-but-2-enedioicacid dimethyl ester, trans-3-phenyl-prop-2-en-1-ol,trans-4-phenyl-but-3-enoic acid methyl ester,2-(acetoxy-phenyl-methyl)-acrylic acid methyl ester,2-(hydroxy-phenyl-methyl)-acrylic acid methyl ester,trans-1,4-dichlorobutene, cis-1,4-dichlorobutene, 2-(phenylp-toluenesulfonamidomethyl)acrylic acid methyl ester and any derivativethereof obtained by substitution of a hydrogen of a C—H bond with analkyl, phenyl, halide, ketone, aldehyde, alcohol, ether, ester,carboxylic acid, primary amino, secondary amino, tertiary amino, amide,nitro, epoxide, aziridine, sulfone, phosphone, and silane, wherein anysaid group can itself be substituted with a said group.
 11. The processof claim 10, wherein compound II is selected from the group consistingof cyclohexene, cyclohex-2-enone, 2-methyl-pent-2-ene,3-bromo-2-methyl-propene, trans-3-phenyl-acrylic acid methyl ester,cyclooctene, 2-methyl-buta-1,3-diene, trans-1,3-diphenylpropenone,trans-hex-4-en-3-one, trans-but-2-enedioic acid dimethyl ester,trans-3-phenyl-prop-2-en-1-ol, trans-4-phenyl-but-3-enoic acid methylester, 2-(acetoxy-phenyl-methyl)-acrylic acid methyl ester,2-(hydroxy-phenyl-methyl)-acrylic acid methyl ester,trans-1,4-dichlorobutene, cis-1,4-dichlorobutene, and 2-(phenylp-toluenesulfonamidomethyl)acrylic acid methyl ester.
 12. The process ofany of claims 1 to 11, wherein R₅ is selected from the group consistingof:

wherein each of R₈, R₉, R₁₀, R₁₁, R₁₂ and R₁₃ is an organic group. 13.The process of claim 12, wherein each of R₈, R₉, R₁₀, R₁₁, R₁₂ and R₁₃is selected from the group consisting of alkyl, alkenyl, alkynyl, aryl,and substituted alkyl, alkenyl, alkynyl, aryl, wherein the substituentsare selected from the group of alkyl, alkenyl, alkynyl, aryl, halide,ketone, aldehyde, alcohol, ether, ester, carboxylic acid, primary amino,secondary amino, tertiary amino, amide, nitrile, nitro, epoxide, imine,aziridine, sulfone, phosphone, and silane.
 14. The process of claim 12,wherein each of R₈, R₉, R₁₀, R₁₁, R₁₂ and R₁₃ is selected from the groupconsisting of alkyl, aryl, phenyl and substituted alkyl, aryl andphenyl, wherein the substituents are selected from the group of alkyl,aryl, phenyl, halide, ketone, aldehyde, alcohol, ether, ester,carboxylic acid, primary amino, secondary amino, tertiary amino, amide,nitro, epoxide, aziridine, sulfone, phosphone, and silane.
 15. Theprocess of claim 14, wherein each of R₈, R₉, R₁₀, R₁₁, R₁₂ and R₁₃includes up to 20 carbon atoms, more preferably up to 18 carbon atoms,more preferably up to 16 carbon atoms, more preferably up to 14 carbonatoms, or up to 12 carbon atoms, or up to 10 carbon atoms, or up to 8carbon atoms, or up to 6 carbon atoms.
 16. The process of claim 13, 14,or 15, wherein each of the substituents of said substituted alkyl andaryl groups from which R₈, R₉, R₁₀, R₁₁, R₁₂ and R₁₃ can be selected isselected from the group consisting of halide, ketone, alcohol and ester.17. The process of any of claims 1 to 16, wherein the compound havingformula III is N-aminophthalmide.
 18. The process of any of claims 1 to17, wherein the compound having formula III has a lower oxidationpotential than that of a compound having formula II.
 19. The process ofany of claims 1 to 17 wherein the compound having formula III isoxidized at a faster rate than a compound having formula II under saidconditions of electrolysis.
 20. The process of any preceding claim,wherein the solvent of the electrolytic cell is a polar non-proticsolvent, and particularly wherein the solvent is selected from the groupconsisting of dichloromethane, acetonitrile, N,N-dimethylformamide,tetrahydrofuran, nitromethane, chloroform, propylene carbonate, andmixtures thereof.
 21. An electrochemical process for the formation of acompound having formula IV,

the process comprising step of: contacting a compound having formula Vand a compound having formula III,

with each other in an electrolytic cell under conditions of electrolysissufficient to form the compound of formula IV, wherein: (i) B isselected from the group consisting of P, S, Se and Te; (ii) each of R₁₄and R₁₅ is hydrogen or an organic group; and (iii) R₅ is NR₆R₇ and eachof R₆ and R₇ is an organic group.
 22. The process of claim 21, wherein Bis a phosphorus atom.
 23. The process of claim 21, wherein B is a sulfuratom.
 24. The process of claim 21, wherein B is an selenium atom. 25.The process of claim 21, wherein B is an tellurium atom.
 26. The processof claim 22, 23, 24 or 25 wherein each of R₁₄, and R₁₅ may be selectedfrom the group consisting of alkyl, alkenyl, alkynyl, aryl, andsubstituted alkyl, alkenyl, alkynyl, aryl, wherein the substituents areselected from the group of alkyl, alkenyl, alkynyl, aryl, halide,ketone, aldehyde, alcohol, ether, ester, carboxylic acid, primary amino,secondary amino, tertiary amino, amide, nitrile, nitro, epoxide, imine,aziridine, sulfone, phosphone, and silane.
 27. The process of claim 26,wherein each of R₁₄, and R₁₅ maybe selected from the group consisting ofalkyl, alkenyl, alkynyl, aryl, and substituted alkyl, alkenyl, alkynyl,aryl, wherein the substituents are selected from the group of alkyl,aryl, halide, ketone, aldehyde, alcohol, ether, ester, carboxylic acid,primary amino, secondary amino, tertiary amino, amide, nitro, epoxide,aziridine, sulfone, phosphone, and silane and preferably wherein each ofR₁₄ and R₁₅ includes up to 20 carbon atoms, more preferably up to 18carbon atoms, more preferably up to 16 carbon atoms, more preferably upto 14 carbon atoms, or up to 12 carbon atoms, or up to 10 carbon atoms,or up to 8 carbon atoms, or up to 6 carbon atoms.
 28. The process ofclaim 27, wherein each of R₁₄, and R₁₅ may be selected from the groupconsisting of alkyl and aryl, and substituted alkyl and aryl, whereinthe substituents are selected from the group of alkyl, aryl, halide,ketone, aldehyde, alcohol, ether, ester, carboxylic acid, primary amino,secondary amino, tertiary amino, amide, nitro, epoxide, aziridine,sulfone, phosphone, and silane.
 29. The process of claim 26, 27 or 28,wherein the substituents are selected from the group of halide, ketone,alcohol and ester.
 30. The process of any of claims 21 to 29, whereincompound V is selected from the group consisting of compounds VIII toXV,

and any derivative of any of compounds VIII to XV obtained bysubstitution of a hydrogen of a C—H bond with an alkyl, phenyl, halide,ketone, aldehyde, alcohol, ether, ester, carboxylic acid, primary amino,secondary amino, tertiary amino, amide, nitro, epoxide, aziridine,sulfone, phosphone, and silane, wherein any said group can itselfinclude such a substituent.
 31. The process of claim 30, whereincompound V is selected from the group consisting of compounds VIII toXV.
 32. The process of any of claims 21 to 31, wherein R₅ is selectedfrom the group consisting of:

wherein each of R₈, R₉, R₁₀, R₁₁, R₁₂ and R₁₃ is an organic group. 33.The process of claim 32, wherein each of R₈, R₉, R₁₀, R₁, R₁₂ and R₁₃ isselected from the group consisting of alkyl, alkenyl, alkynyl, aryl, andsubstituted alkyl, alkenyl, alkynyl, aryl, wherein the substituents areselected from the group of alkyl, alkenyl, alkynyl, aryl, halide,ketone, aldehyde, alcohol, ether, ester, carboxylic acid, primary amino,secondary amino, tertiary amino, amide, nitrile, nitro, epoxide, imine,aziridine, sulfone, phosphone, and silane.
 34. The process of claim 32,wherein each of R₈, R₉, R₁₀, R₁₁, R₁₂ and R₁₃ is selected from the groupconsisting of alkyl, aryl, phenyl and substituted alkyl, aryl andphenyl, wherein the substituents are selected from the group of alkyl,aryl, phenyl, halide, ketone, aldehyde, alcohol, ether, ester,carboxylic acid, primary amino, secondary amino, tertiary amino, amide,nitro, epoxide, aziridine, sulfone, phosphone, and silane.
 35. Theprocess of claim 34, wherein each of R₈, R₉, R₁₀, R₁₁, R₁₂ and R₁₃includes up to includes up to 20 carbon atoms, more preferably up to 18carbon atoms, more preferably up to 16 carbon atoms, more preferably upto 14 carbon atoms, or up to 12 carbon atoms, or up to 10 carbon atoms,or up to 8 carbon atoms, or up to 6 carbon atoms.
 36. The process ofclaim 33, 34, or 35, wherein each of the substituents of saidsubstituted alkyl and aryl groups from which R₈, R₉, R₁₀, R₁, R₁₂ andR₁₃ can be selected is selected from the group consisting of halide,ketone, alcohol and ester.
 37. The process of any of claims 21 to 36,wherein the compound having formula III is N-aminophthalimide.
 38. Theprocess of any of claims 21 to 37, wherein the compound having formulaIII has a lower oxidation potential than that of a compound havingformula II.
 39. The process of any of claims 21 to 37 wherein thecompound having formula III is oxidized at a faster rate than a compoundhaving formula II under said conditions, of electrolysis.
 40. Theprocess of any of claims 21 to 39, wherein the solvent of theelectrolytic cell is a polar non-protic solvent, and particularlywherein the solvent is selected from the group consisting ofdichloromethane, acetonitrile, N,N-dimethylformamide, tetrahydrofuran,nitromethane, chloroform, propylene carbonate, and mixtures thereof. 41.An electrochemical process for the formation of a compound havingformula VI,

the process comprising step of: contacting a compound having formula VIIand a compound having formula III,

with each other in an electrolytic cell under conditions of electrolysissufficient to form the compound of formula VI, wherein: (i) when D is acarbon atom, each of R₁₆ and R₁₇ is hydrogen or an organic group; and(ii) when D is a nitrogen atom, R₁₆ is hydrogen or an organic group, andR₁₇ is an electron pair.
 42. The process of claim 41, wherein D is acarbon atom.
 43. The process of claim 41, wherein D is a nitrogen atom.44. The process of claim 42 or 45 wherein each of R₁₆, and R₁₇ may beselected from the group consisting of alkyl, alkenyl, alkynyl, aryl, andsubstituted alkyl, alkenyl, alkynyl, aryl, wherein the substituents areselected from the group of alkyl, alkenyl, alkynyl, aryl, halide,ketone, aldehyde, alcohol, ether, ester, carboxylic acid, primary amino,secondary amino, tertiary amino, amide, nitrile, nitro, epoxide, imine,aziridine, sulfone, phosphone, and silane, and preferably wherein eachof R₁₆ and R₁₇ includes up to 20 carbon atoms, more preferably up to 18carbon atoms, more preferably up to 16 carbon atoms, more preferably upto 14 carbon atoms, or up to 12 carbon atoms, or up to 10 carbon atoms,or up to 8 carbon atoms, or up to 6 carbon atoms.
 45. The process ofclaim 44, wherein each of R₁₆, and R₁₇ maybe selected from the groupconsisting of alkyl, alkenyl, alkynyl, aryl, and substituted alkyl,alkenyl, alkynyl, aryl, wherein the substituents are selected from thegroup of alkyl, aryl, halide, ketone, aldehyde, alcohol, ether, ester,carboxylic acid, primary amino, secondary amino, tertiary amino, amide,nitro, epoxide, aziridine, sulfone, phosphone, and silane.
 46. Theprocess of claim 45, wherein each of R₁₆, and R₁₇ may be selected fromthe group consisting of alkyl and aryl, and substituted alkyl and aryl,wherein the substituents are selected from the group of alkyl, aryl,halide, ketone, aldehyde, alcohol, ether, ester, carboxylic acid,primary amino, secondary amino, tertiary amino, amide, nitro, epoxide,aziridine, sulfone, phosphone, and silane.
 47. The process of claim 44,45 or 46, wherein the substituents are selected from the group ofhalide, ketone, alcohol and ester.
 48. The process of any of claims 41to 47, wherein R₅ is selected from the group consisting of:

wherein each of R₈, R₉, R₁₀, R₁₁, R₁₂ and R₁₃ is an organic group. 49.The process of claim 48, wherein each of R₈, R₉, R₁₀, R₁₁, R₁₂ and R₁₃is selected from the group consisting of alkyl, alkenyl, alkynyl, aryl,and substituted alkyl, alkenyl, alkynyl, aryl, wherein the substituentsare selected from the group of alkyl, alkenyl, alkynyl, aryl, halide,ketone, aldehyde, alcohol, ether, ester, carboxylic acid, primary amino,secondary amino, tertiary amino, amide, nitrile, nitro, epoxide, imine,aziridine, sulfone, phosphone, and silane.
 50. The process of claim 48,wherein each of R₈, R₉, R₁₀, R₁₁, R₁₂ and R₁₃ is selected from the groupconsisting of alkyl, aryl, phenyl and substituted alkyl, aryl andphenyl, wherein the substituents are selected from the group of alkyl,aryl, phenyl, halide, ketone, aldehyde, alcohol, ether, ester,carboxylic acid, primary amino, secondary amino, tertiary amino, amide,nitro, epoxide, aziridine, sulfone, phosphone, and silane.
 51. Theprocess of claim 50, wherein each of R₈, R₉, R₁₀, R₁₁, R₁₂ and R₁₃includes up to includes up to 20 carbon atoms, more preferably up to 18carbon atoms, more preferably up to 16 carbon atoms, more preferably upto 14 carbon atoms, or up to 12 carbon atoms, or up to 10 carbon atoms,or up to 8 carbon atoms, or up to 6 carbon atoms.
 52. The process ofclaim 49, 50, or 51, wherein each of the substituents of saidsubstituted alkyl and aryl groups from which R₈, R₉, R₁₀, R₁₁, R₁₂ andR₁₃ can be selected is selected from the group consisting of halide,ketone, alcohol and ester.
 53. The process of any of claims 41 to 52,wherein the compound having formula II is N-aminophthalimide.
 54. Theprocess of any of claims 41 to 53, wherein the compound having formulaIII has a lower oxidation potential than that of a compound havingformula II.
 55. The process of any of claims 41 to 53 wherein thecompound having formula III is oxidized at a faster rate than a compoundhaving formula II under said conditions of electrolysis.
 56. The processof any of claims 41 to 55, wherein the solvent of the electrolytic cellis a polar non-protic solvent, and particularly wherein the solven isselected from the group consisting of dichloromethane, acetonitrile,N,N-dimethylformamide, tetrahydrofuran, nitromethane, chloroform,propylene carbonate, and mixtures thereof.
 57. An electrochemicalprocess of any preceding claim wherein said contacting step includescontacting said compounds with each other in an anode compartment ofsaid electrolytic cell in an anolyte which comprises a carboxylate ion.58. The process of claim 57, wherein the anolyte solution issubstantially free of a metal catalyst.
 59. The process of claim 58,wherein said metal is selected from the group of lead cadmium, cerium,cobalt, chromium, copper, ion, mercury, iridium, manganese, molybdenum,nickel, osmium, palladium, rhenium, rhodium, ruthenium, antimony,thallium, tin and vanadium.
 60. The process of any of claims 57 to 59,wherein said anode a platinum electrode.
 61. The process of any ofclaims 57 to 60, wherein an acid form of said carboxylate has a firstpK_(a), and said anolyte solution further comprises an acid having asecond pK_(a) wherein said second pK_(a) exceeds the first pK_(a). 62.The process of claim 61 wherein the carboxylate and the acid having thesecond pK_(a) are solubilized in the solution and the carboxylate isprovided in solution in a stoichiometric amount equal to at least halfthat of the hydrazine derivative.
 63. The process of claim 62 whereinthe acid form of said carboxylate has the formula RCO₂H wherein R is anorganic group.
 64. The process of claim 62 wherein the acid for of saidcarboxylate has the formula RCO₂H wherein R is an alkyl group or ahaloalkyl group.
 65. The process of any of claims 61 to 64 wherein thefirst pK_(a) is in the range of about −2 to about +7.
 66. The process ofclaim 65 wherein the first pK_(a) is in the range of about −1 to about+6.
 67. The process of claim 66 wherein the first pK_(a) is in the rangeof about 0 to about +5.
 68. The process of claim 67 wherein the firstpK_(a) is about 0.3.
 69. The process of claim 67 wherein the firstpK_(a) is about 2.8.
 70. The process of claim 67 wherein the firstpK_(a) is about 4.8.
 71. The process of any of claims 57 to 65, whereinsaid carboxylate is selected from the group acetate, trifluoroacetate,and monochloroacetate.
 72. The process of any of claims 61 to 71,wherein said acid is an ammonium acid and said second pK_(a) exceeds thefirst pK_(a) by at least
 2. 73. The process of claim 72, wherein saidammonium acid has the formula R₁R₂R₃NH⁺ wherein each of R₁, R₂ and R₃ isan organic group or hydrogen.
 74. The process of claim 73, wherein eachof R₁, R₂ and R₃ of the ammonium acid is an alkyl group or hydrogen. 75.The process of any of claims 61 to 63, wherein said acid having thesecond pK_(a) is triethylammonium.
 76. The process of any of claims 57to 75, wherein the carboxylate is provided in solution in astoichiometric amount about equal to that of the hydrazine derivative.77. The process of any of claims 57 to 76, wherein the anolyte solutionfurther comprises a counterion to the carboxylate, the counterion havingthe formula R₁R₂R₃ R₄ N⁺ wherein each of R₁, R₂, R₃, and R₄ is anorganic group.
 78. The process of claim 77, wherein each said organicgroup of the counterion is an alkyl group or a haloalkyl group.
 79. Theprocess of claim 78, wherein each said organic group of the counterionis an alkyl group.
 80. The process of claim 79, wherein each saidorganic group of the counterion is an alkyl group selected from thegroup of methyl, ethyl, propyl, butyl and pentyl.
 81. The process of anypreceding claim, wherein said contacting step is carried out in ananodic half cell divided from and operatively linked to a cathodic halfcell.
 82. The process of claim 81, wherein said half cells are linked byan ion permselective diaphragm.
 83. The process of claim 82 wherein saiddiaphragm comprises a synthetic polymer having anions affixed thereto.84. The process apparatus of claim 83, wherein said anions includeperfluorosulfonate groups.
 85. The process of claim 84, wherein saiddiaphragm comprises a Nafion membrane.
 86. The process of any precedingclaim, wherein compound II, V, or VII, as the case may be, has a morepositive potential than the voltage at which the contacting step isconducted.
 87. The process of claim 86 wherein compound III has firstand second peak potentials, each of which potentials is between about 0and 3 volts against Ag/AgCl, more preferably between about 1 and 2volts.
 88. The process of any preceding claim wherein the mole ratio ofthe compound having formula Im to the compound having formula II, V, orVU, as the case may be, is from about 1:1 to about 1000:1; morepreferably between 500:1 and 1:1; more preferably between about 100: and1:1; more preferably between about 25:1 and 1:1; more preferably betweenabout 10:1 and 1:1; more preferably between about 5:1 and 1:1, morepreferably between about 2:1 and 1:1.
 89. The process of any precedingclaim wherein the electric potential applied during the contacting stepis applied for a period between about 1 minute and 10 hours.
 90. In aprocess of addition of a nitrogen across a multiple bond of an organicmolecule wherein a first atom of the multiple bond is a carbon atom, andthe second atom is selected from the group of carbon, oxygen andnitrogen, the improvement comprising electrochemically generating thenitrogen for the addition from a primary hydrazine derivative in thepresence of a carboxylate anion.
 91. The process of claim 90, whereinthe nitrogen is generated from a compound having the structure indicatedby formula III, as defined in any of claims 1 and 12 to
 17. 92. Theprocess of claim 91, wherein the organic molecule has the structureindicated by formula I as defined in any of claims 1 to 11, or formulaVII as defined in any of claims 41 to
 47. 93. In a process of additionof a nitrogen to a heteroatom of an organic molecule wherein theheteroatom forms a double bond with an oxygen atom and is a P, S, Se orTe atom, the improvement comprising electrochemically generating thenitrogen for the addition from a primary hydrazine derivative in thepresence of a carboxylate anion.
 94. The process of claim 93, whereinthe nitrogen is generated from a compound having the structure indicatedby formula HI, as defined in any of claims 1 and 12 to
 17. 95. Theprocess of claim 94, wherein the organic molecule has the structureindicated by formula V as defined in any of claims 21 to
 29. 96. Aproduct when obtained by a process defined by any preceding claim.
 97. Aprocess for electrochemically generating a nitrene, the processcomprising the step of: exposing a hydrazine derivative contained in ananolyte solution of an electroytic cell to the anode of the cell in thepresence of a carboxylate ion, wherein one of the nitrogens of thehydrazine group is a primary amino group.
 98. The process of claim 97,wherein the anolyte solution is substantially free of a metal catalyst.99. The process of claim 98, wherein said metal is selected from thegroup of lead cadmium, cerium, cobalt, chromium, copper, ion, mercury,iridium, manganese, molybdenum, nickel, osmium, palladium, rhenium,rhodium, ruthenium, antimony, thallium, tin and vanadium.
 100. Theprocess of any of claims 97 to 99, wherein said anode a platinumelectrode.
 101. The process of any of claims 97 to 100, wherein an acidform of said carboxylate has a first pK_(a), and said anolyte solutionfurther comprises an acid having a second pK_(a) wherein said secondpK_(a) exceeds the first pK_(a).
 102. The process of claim 101 whereinthe carboxylate and the acid having the second pK_(a) are solubilized inthe solution and the carboxylate is provided in solution in astoichiometric amount equal to at least half that of the hydrazinederivative.
 103. The process of claim 102 wherein the acid form of saidcarboxylate has the formula RCO₂H wherein R is an organic group. 104.The process of claim 102 wherein the acid for of said carboxylate hasthe formula RCO₂H wherein R is an alkyl group or a haloalkyl group. 105.The process of any of claims 101 to 104 wherein the first pK_(a) is inthe range of about −2 to about +7.
 106. The process of claim 105 whereinthe first pK_(a) is in the range of about −1 to about +6.
 107. Theprocess of claim 106 wherein the first pK_(a) is in the range of about 0to about +5.
 108. The process of claim 107 wherein the first pK_(a) isabout 0.3.
 109. The process of claim 107 wherein the first pK_(a) isabout 2.8.
 110. The process of claim 107 wherein the first pK_(a) isabout 4.8.
 111. The process of any of claims 97 to 105, wherein saidcarboxylate is selected from the group acetate, trifluoroacetate, andmonochloroacetate.
 112. The process of any of claims 101 to 111, whereinsaid acid is an ammonium acid and said second pK_(a) exceeds the firstpK_(a) by at least
 2. 113. The process of claim 112, wherein saidammonium acid has the formula R₁R₂R₃NH⁺ wherein each of R₁, R₂ and R₃ isan organic group or hydrogen.
 114. The process of claim 113, whereineach of R₁, R₂ and R₃ of the ammonium acid is an alkyl group orhydrogen.
 115. The process of any of claims 101 to 103, wherein saidacid having the second pK_(a) is triethylammonium.
 116. The process ofany of claims 97 to 115, wherein the carboxylate is provided in solutionin a stoichiometric amount about equal to that of the hydrazinederivative.
 117. The process of any of claims 97 to 116, wherein theanolyte solution further comprises a counterion to the carboxylate, thecounterion having the formula R₁R₂R₃ R₄ N⁺ wherein each of R₁, R₂, R₃,and R₄ is an organic group.
 118. The process of claim 117, wherein eachsaid organic group of the counterion is an alkyl group or a haloalkylgroup.
 119. The process of claim 118, wherein each said organic group ofthe counterion is an alkyl group.
 120. The process of claim 119, whereineach said organic group of the counterion is an alkyl group selectedfrom the group of methyl, ethyl, propyl, butyl and pentyl.
 121. Theprocess of any of claims 97 to 120 wherein said hydrazine derivativecomprises a molecule having the structure indicated as formula Im asdefined in any of claims 1 and 12 to
 17. 122. The process of any ofclaims 97 to 121, wherein the anolyte solution comprises a solvent asdefined in claim
 20. 123. An apparatus for electrochemical generation ofa nitrene, the apparatus comprising: an anodic half cell operativelylinked to a cathodic half cell; and an anolyte solution comprising acarboxylate anion and a primary hydrazine derivative.
 124. The apparatusof claim 123, wherein said half cells are linked by an ion permselectivediaphragm.
 125. The apparatus of claim 124, wherein said diaphragmcomprises a synthetic polymer having anions affixed thereto.
 126. Theapparatus of claim 125, wherein said anions include perfluorosulfonategroups.
 127. The apparatus of claim 126, wherein said diaphragmcomprises a Nafion membrane.
 128. The apparatus of any of claims 123 to127, wherein the hydrazine has a formula im as defined in any of claims1 and 5 to
 17. 129. The apparatus of any of claims 123 to 128, whereinthe anolyte solution is substantially free of a metal catalyst.
 130. Theapparatus of claim 129, wherein said metal is selected from the group oflead cadmium, cerium, cobalt, chromium, copper, ion, mercury, iridium,manganese, molybdenum, nickel, osmium, palladium, rhenium, rhodium,ruthenium, antimony, thallium, tin and vanadium.
 131. The apparatus ofany of claims 123 to 130, wherein said anode a platinum electrode. 132.The apparatus of any of claims 123 to 131, wherein an acid form of saidcarboxylate has a first pK_(a), and said anolyte solution furthercomprises an acid having a second pK_(a) wherein said second pK_(a)exceeds the first pK_(a).
 133. The apparatus of claim 132 wherein thecarboxylate and the acid having the second pK_(a) are solubilized in thesolution and the carboxylate is provided in solution in a stoichiometricamount equal to at least half that of the hydrazine derivative.
 134. Theapparatus of claim 133 wherein the acid form of said carboxylate has theformula RCO₂H wherein R is an organic group.
 135. The apparatus of claim133 wherein the acid for of said carboxylate has the formula RCO₂Hwherein R is an alkyl group or a haloalkyl group.
 136. The apparatus ofany of claims 132 to 135 wherein the first pK_(a) is in the range ofabout −2 to about +7.
 137. The apparatus of claim 136 wherein the firstpK_(a) is in the range of about −1 to about +6.
 138. The apparatus ofclaim 137 wherein the first pK_(a) is in the range of about 0 to about+5.
 139. The apparatus of claim 138 wherein the first pK_(a) is about0.3.
 140. The apparatus of claim 138 wherein the first pK_(a) is about2.8.
 141. The apparatus of claim 138 wherein the first pK_(a) is about4.8.
 142. The apparatus of any of claims 123 to 136, wherein saidcarboxylate is selected from the group acetate, trifluoroacetate, andmonochloroacetate.
 143. The apparatus of any of claims 132 to 142,wherein said acid is an ammonium acid and said second pK_(a) exceeds thefirst pK_(a) by at least
 2. 144. The apparatus of claim 143, whereinsaid ammonium acid has the formula R₁R₂R₃NH⁺ wherein each of R₁, R₂ andR₃ is an organic group or hydrogen.
 145. The apparatus of claim 144,wherein each of R₁, R₂ and R₃ of the ammonium acid is an alkyl group orhydrogen.
 146. The apparatus of any of claims 132 to 134, wherein saidacid having the second pK_(a) is triethylammonium.
 147. The apparatus ofany of claims 123 to 146, wherein the carboxylate is provided insolution in a stoichiometric amount about equal to that of the hydrazinederivative.
 148. The apparatus of any of claims 123 to 147, wherein theanolyte solution further comprises a counterion to the carboxylate, thecounterion having the formula R₁R₂R₃ R₄ N⁺ wherein each of R₁, R₂, R₃,and R is an organic group.
 149. The apparatus of claim 148, wherein eachsaid organic group of the counterion is an alkyl group or a haloalkylgroup.
 150. The apparatus of claim 149, wherein each said organic groupof the counterion is an alkyl group.
 151. The apparatus of claim 149,wherein each said organic group of the counterion is an alkyl groupselected from the group of methyl, ethyl, propyl, butyl and pentyl. 152.A process for screening an olefin for electrochemical aziridination ofan olefin with a hydrazine derivative, the process comprising the stepsof: providing the olefin; determining the redox potential of the olefinat a predetermined voltage at which the aziridine derivative isoxidized, wherein a said olefin determined to have a less positivepotential than the predetermined voltage is eliminated as a candidatefor electrochemical aziridination by said hydrazine derivative.
 153. Aprocess for screening an olefin for electrochemical aziridination of anolefin with a hydrazine derivative, the process comprising the steps of:providing the olefin; determining the redox potential of the olefin at apredetermined voltage at which the aziridine derivative is oxidized,wherein a said olefin determined to have a more positive potential thanthe predetermined voltage is selected as a candidate for electrochemicalaziridination by said hydrazine derivative.
 154. The process of claim152 or 153, wherein said hydrazine derivative has first and second peakpotentials, each of which potentials is between about 0 and 3 voltsagainst Ag/AgCl.
 155. The process of claim 154, wherein said hydrazinederivative has first and second peak potentials, each of whichpotentials is between about 0 and 3 volts against Ag/AgCl.